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By Vaughan R. Voller

"Over the last ten years an increasing number of heat and mass transfer models of solidification processes have been presented in the literature. A key component in these models is the coupling between thermal and solute fields. This is achieved by developing relationships based on the behavior at the microscopic scale in the casting (typically a secondary dendrite arm space). An important class of models in this respect are models that describe the local scale redistribution of solute alloy components-collectively referred to as microsegregation models. This paper explores this class of models.IntroductionModeling takes a key role in processing materials for properties. This is particularly time in solidification processes where current computer techniques allow for a detailed treatment of the critical macroscopic phenomena. Typically these macro scale models consist ·of three main coupled components.1. A model of flow in the melt and solid + liquid mushy region.2. A model of heat transfer.3. A model of solute transport.The focus of this paper is the solute transport component, in particular the manner in which process scale transport is coupled to transport ·at the local scale of the solid-liquid interface. This step requires a modeling of the redistribution of solutes at the scale of the secondary arm spaces in the dendritic mushy region-a process referred to as microsegregation. Basic microsegregation models use the limit assumptions of no mass diffusion in the solid (Gulliver-Scheil [l]) or complete diffusion in the solid (equilibrium lever rule) in a fixed and space. Recently, however, more sophisticated microsegregation models that account for finite mass diffusion and coarsening of the arm space have been developed [2-19]. In this paper governing equations for a general microsegregation model for a multi-component alloy in a coarsening and spacing _are introduced. From these general equations various models for a binary system are developed and tested"

Jan 1, 2000

By K. Osseo-Asare

Rate laws for the hydrogen reduction of metal ions are typically of the form: [r = -d[M(II)]/dt = k[M(II)]xPy2H] where k is an apparent rate constant, [M(II)] and PH2 represent dissolved metal concentration and hydrogen pressure respectively, while x = 0 - 1 and y = 0.5 - 2. Half-order dependences have been reported for some M(II)/H2 systems; however, no satisfactory explanations have been offered. In an effort to bridge this gap in our understanding, the published precipitation rate data (for M(II) = Cu(II), Ni(II), and Co(II)) are reviewed (with emphasis on the reported reaction orders) and compared with the corresponding but limited electrochemical polarization data. Based on the available literature on the electrochemical kinetics of the M/M(II) and H2/H+ systems it is demonstrated theoretically that, under certain conditions (e.g., in the presence of electron-conducting solids), the rate of the M(II)/H2 reaction can be expressed as: [-d[M2+]/dt = k[M2+]2/1P2/12H] It is concluded that electrochemical processes probably play an important role in the hydrogen reduction of metal ions, especially for systems that involve heterogeneous catalysis.

Jan 1, 2003

By Jaeheon Lee

Gold-copper alloys are shown to form during the cementation of gold on copper in a solution containing 0.25M [S2O32-] at 25oC. The alloy composition is strongly dependent on the initial Cu:Au ratio in solution and ranges from Au3Cu to AuCu3. XPS results for Au, Cu, S, and O are reported as a function of depth through an entire deposited film with an initial solution containing 20 ppm [Au] and 30 ppm [Cu]. The deposit contained about 20 atomic % gold and was predominantly Cu3Au. Underpotential deposition (UPD) theory is discussed as a mechanism for explaining the formation of these alloys. Several other systems that produce alloys during contact reduction/cementation are also discussed.

Jan 1, 2003

By Gordon Irons, Kevin Graham, Krishnakumar Krishnapisharody

Ladle or secondary metallurgy in steelmaking is an essential process step for the production of high-quality steel. Professor David Robertson was a pioneer in the modeling of these processes, in particular gas-metal fluid dynamic interactions and the rates of slag-metal reactions. This is now a highly active area of research, and some of the recent developments in this area will be reviewed.

Jan 1, 2014

By Hector M. Henao

There is an increasing trend in the copper smelters to recycle electronic materials, which contain relatively high concentration of precious metals. As a consequence, the amount of precious metals lost in the slag phase is increasing. To determine the portion of the precious metals chemically dissolved and that associated with the mechanically trapped matte in the slag will be a key factor to improve the recovery of those metals. Thus, an experimental study was carried out to determine the distribution of precious metals (Au, Pt, Pd, Rh, Ru) between the equilibrated copper matte and iron-silicate slag phases. The experiments were made in a magnesia crucible at 1573 K and a fixed partial pressure of SO2 of 0.1 atm for the matte grades between 40 and 70 mass% of copper. It was found that the distribution ratios (defined as mass% X in slag/mass% X in matte, where X represents the precious metal) are around 10-2 for Ru, 10-3 for Au, Pt and Pd and 10-4 for Rh. The distribution ratios show a tendency to increase when the grade of matte is increased.

Jan 1, 2006

By U. M. Mutnti

In order to meet the stringent market requirements for high purity cobalt, ZCCM commissioned the VIR plant in December 1982. The plant comprises a 4.1 tonne/heat vacuum induction furnace with a rated annual capacity of 2,500 MT of barstock. In the VIR furnace, molten cobalt is held under vacuum at 1600°C resulting in the removal of more volatile impurity elements by distillation. Operations todate have demonstrated that Pb, Zn and Cd have good distillation rates in excess of 95%, leading to cobalt containing 1 ppm or less of the above elements. Removal of other impurities such as Se, Bi is about 65% with the finished product still assaying around 1 ppm of each of these elements. Vacuum refining of cobalt offers an economic route for producing higher grades of cobalt from the type of concentrates and treatment processes available within ZCCM. The consistency of VIR cobalt quality has been confirmed by ZCCM and some of its alloy customers.

Jan 1, 1988

By R. Harris

Blister copper melts of 800 g to 1000 g containing less than 1 wt % S and up to 3 wt % Ni were desulfurized at 1523 K in air or by a pure oxygen jet blown at 75,500 and 1000 cm3/min, from 1 cm above the melt. Rates of desulfurization and oxygen pickup were measured and visible surface phenomena were photographed and videotaped. It was observed that SO2 was evolved from Cu-S melts in a manner reminiscent of the effervescence seen in carbonated drinks. The effervescence lasted up to 20 minutes and resulted in the ejection of material up to a height 50 cm above the melt surface. Sporadic discharge of large bubbles was also observed in a Ni containing melt top-blown with oxygen at 1000 cm3/min. The Cu-S melts top-blown with oxygen experienced faster sulfur elimination as compared to stagnant melts exposed to air and experienced only a single period of turbulent SO2 evolution, which occurred almost immediately after oxygen injection commenced. The Cu-S melts exposed to air experienced multiple episodes of effervescence. The stagnant blister copper melt containing nickel did not exhibit effervescent behaviour and experienced a lower rate of sulfur elimination compared to Cu-S melts tested under similar conditions. The present article examines the role of surface phenomena in determining the observed behaviour.

Jan 1, 1999

By I. D. Reznik

On blowing nickel matte in a converter without quartz, first the oxidation of metallic iron and a part of FeS occurs without evolving sulfur dioxide, the formed FeO dissolves in a sulphide smelt and form a homogeneous oxysulphide smelt. On further increasing the FeO content, the oxysulphide separates into 2 layers. Based on the laboratory investigation of FeO-(FeS+Fe°) - (Ni3S2+Ni°) ternary phase diagram we have identified the separation region at 1250°C. The boundaries of the separation region have the form of an arc and the composition of the separated oxysulphide layers is defined by the canodes. In the nickel or copper-nickel matte - silicacalcium oxide slag system at 1250°C three layers, namely sulphide, oxysulphide, and slag may be formed. A high slag basicity due to the presence of CaO can serve to enhance the activity of FeO; a low nickel content in the matte corresponds to a high concentration of FeS therein; FeO from slag and FeS from the matte form a homogeneous FeO-FeS solution, i.e. an oxysulphide layer. The investigation on the "Camebaks" apparatus and by the nuclear gamma-ray resonance spectroscopy method of the phase composition in a slowly cooled oxysulphide layer has shown the presence of four phases: wustite, troilite, ferronickel grains, and calcium oxide-silica inclusions. Knowledge of regularities in the oxysulphides formation makes it possible to use them in pyrometallurgy of nickel and cobalt or preventing their formation.

Jan 1, 1997

By Julian Johnson

The effect of changing redox potential (Eh) on the high temperature sulfuric acid leaching of Western Australian dry-land nickel laterite ores has been investigated. In particular, the effect of added reductant (sulfur, sodium sulfite) or oxidant (potassium chromate) on Eh, leaching kinetics, metal extractions, acid utilisation and leach residues has been determined. Three separate ores - nonhonitic ores from Murrin Mumn and Bulong, and limonitic ore from Cawse - were used in the study. Sulfur addition varied from 0 to 7.8 kg/t ore. The total acid loading was kept constant at 430 kg/t (Murrin Murrin ore) and 330 kglt (Cawse ore), whilst acid loading for Bulong ore was varied according to the presence of either reductant or oxidant. The extraction of both nickel and cobalt from limonite ore remained unaffected when small amounts of sulfkr were added, but addition of even small amounts of reductant to nontronitic ore decreased both nickel and cobalt extraction. Increased manganese and iron dissolution were observed as the levels of reductant increased, accompanied by a decrease in chromium dissolution. As the iron dissolution increased, free acidity decreased, with a subsequent decrease in nickel extraction. In contrast, addition of oxidant lead to reduced iron and manganese dissolution and slower extraction of nickel and cobalt. Keywords: Limonite, Nonhonite, Eh, Nickel Extraction

Jan 1, 2004

By R. M. Cunningham

Asarco operates one of the largest individual copper electrolytic refineries in the world at Amarillo, Texas. The feed for this refinery is a mixture of anodes produced at Asarco smelters and copper purchased t?om a number of primary and secondary sources. The variation in feed makes it imperative that the refinery practices state-of-the-art quality control to minimize the effects'of unwanted impurities in the electrolytic refining process. In late 1993, a plant designed to sigru6cantly reduce the antimony and bismuth levels in the electrolyte was commissioned. The purification plant uses ion exchange technology in conjunction with a novel strippiing system developed by Zeneca Specialties (U.K.). The strippiing system permits the recycling of the eluant and thus avoids the extremely high costs of stripping with conventional reagents. In addition, the environmental impact of treating the eluant for recovery of antimony and bismuth is minimized. This paper outlines the development of the technology and, in particular, describes the operational practices and improvements at Amarillo since the commissioning of the plant.

Jan 1, 1997

By Mingchun Lu, Yunjin Yan

"This paper describes a new type of bell-less top installed on two relined blast furnaces at Tianjin Iron Works and another new-built at Echeng Steel Works in China. A compact installation was presented for existing furnace top innovation with the least reformation of existing top structure. A water cooling and sealing gearbox used for driving the chute discards completely the traditional idea about necessity of continuous supply of cooling gas for the gearbox. A multiring spreader and its dozens of selectable charging patterns enables an operator to achieve optimal burden distribution easily under the condition of a minimum investment of control equipment. Some useful conclusions have been made through a small-size model and a full-scale model tests. The excellent characteristics and the superiority of the new top have been fully proved at both works.IntroductionIt is known that there are some advantages with the bell-less top of a blast furnace: suitable for furnace to operate at high top pressure, capable of realizing optimal burden distribution, less investment and maintenance costs, etc. But why do most of blast furnaces in the world still remain using conventional bell top. One of the concerns is that current bell-less tops still have some shortcomings:1) The height of a current bell-less top might be lower than three or four-bell top or two-bell plus valve seal top, but still much higher than an ordinary two-bell top.2) The gearbox for driving the rotating chute is positioned onto the lip of the furnace. It is subject to attack by crude hot bf gas. Continuously pumping cooling gas (pressurized nitrogen or clean bf gas) into the gearbox is indispensable to withstand such a harsh working environment. Therefore, a plant furnished with blower8 and its ancillaries has to be built, It involves a large sum of investment and much expense in its annual running costs.3) Although the current bell-less charging device as a means of controlling burden distribution possesses a wide range of freedom, it is difficult to realize optimal burden distribution. There are some large blast furnaces realized better burden distribution, but sophisticated control means is indispensable so that the investment of control means is much higher."

Jan 1, 2000

By Stanko Nikolic

Ferrous calcium silicate slags are potentially important for future practice in copper converting operations and processes and can be described by the ?Cu2O?-FeO-Fe2O3-CaO-SiO2 system. Despite its industrial importance the phase equilibria in this system have not been fully investigated. Characterization of this slag system is necessary to improve the design and optimization parameters of new processes, including fluxing and operating temperatures. Experimental methods have been developed to investigate the phase equilibria of these slags at copper saturation and without copper. This technique involved equilibration of samples at a fixed oxygen partial pressure, rapid quenching, and analysis of the compositions of phases using electron probe x-ray microanalysis (EPMA). Liquidus and solidus data are reported for the primary phase fields of spinel, wollastonite and tridymite at 1250oC and an oxygen partial pressure of 10-6atm. The resulting data has been used to construct liquidus isotherms in the ?FeO?-CaO-SiO2 system both in equilibrium with and without molten copper. The experimental results were compared with the predictions of a thermodynamic computer package utilizing a self consistent thermodynamic database. The predictions of the model were in good agreement with the experimental isotherms when projected onto the FeO-CaO-SiO2 section, however the copper concentrations in the liquid phase at copper saturation were lower than predicted using the current database of the model.

Jan 1, 2006

By Robert L. Opila

Negative electrodes for alkaline nickel-metal hydride batteries composed of MmNi3.5Al0.8Co0.7, where Mm is misch metal, have been characterized electrochermically and using x-ray photoelectron spectroscopy. The stability and rapid hydriding and dehydriding kinetics of the alloy in KOH are attibuted to a surface film. The protective surface film is shown to consist of an porous, outer hydrated layer and a dense, inner oxide layer. In addition, metallic nickel and cobalt are found throughout the film, and are presumed to form a conductive, percolative network that permits rapid electron transfer from the bulk to the solution, allowing rapid electrochemical formation of atomic hydrogen.

Jan 1, 1997

By Zhenjun Tan, Lei Zhang, Jigang Li, Yifang Zheng, Jilai Xue

"Water electrolysis in 0.4 mol/L NaOH solution for hydrogen generation was carried out with ultrasound introduced through the anode. It was found that the cell voltage reduced by 150-300 mV in the current range of 20 mA to 40 mA with ultrasound frequency at 25.3 kHz. The cell operation became unstable when the cell current was larger than 75 mA with ultrasound. This reduction in cell voltage was due to removal of the gas bubbles on the electrode surface, which can be directly observed in the see-through cell of water electrolysis. Ultrasound with frequency of 33.3 Hz was also tried, but no better effect was obtained. The results suggest that ultrasound assisted water electrolysis can have potential in energy savings for hydrogen production.IntroductionIn electrolytic process, the electrode that the bubbles generated on its surface usually covered a thin gas film, which can be caused an additional voltage about 0.15-0.25V[l,2], especially in aluminum electrolysis. To solve the problem, loading the ultrasound removes the gas bubbles from the electrodes, this subject had been researched in recent years. From 1995 Jilai Xue et al[3,4,5]. applied the ultrasound in aluminum electrolysis in lab. The results from Sheng-De Li et al.[6] reveals that can decrease the cell voltage and have influences about the hydrogen and oxygen's output ratio. Although there are many paper about the applying of ultrasound such as in electrolysis[5,6], deposition[7,8], plating[9,10], oxidation of salts substance on the surface of electrodes[l 1] and so on, the effect of different frequencies ultrasound hadn't been investigated deeply.We focus on the anode voltage by different frequencies ultrasound and the bubble behaviors in this paper. The environment of this experiment is in alkaline solution. Through this exploration it can offer a basis for the applying of ultrasound in electrolysis."

Jan 1, 2011

By Harry Littleton, Jr. Scarber, Wanliang Sun

"The Lost Foam Casting (LFC) process is relatively immature when compared to other casting processes. To make the process more robust, computer modeling is needed to reduce lead times and casting defects. In this study, metal filling of lost foam aluminum castings was visualized using state-of-art real time X-Ray technology. Metal filling of the lost foam casting was simulated using a commercial software package. The result of the computer simulation was compared with the results of the real time X-Ray visualization. Some of the computer simulation results agreed with the real time X-Ray visualization, but some did not. Based on other studies using real time X-Ray technology, new input variables, such as foam density variations, were developed for the computer modeling. With the new variables, modeling of the lost foam casting process becomes more realistic. IntroductionMold filling of the Lost Foam Casting (LFC) process is an important step toward making a quality part. In the LFC process, molten metal is poured against a refractory coated foam pattern surrounded by dry sand. At the pouring temperature of aluminum, the foam pattern is decomposed into 30% (wt) gaseous and 70% (wt) liquid foam pyrolysis products. Existence of the gaseous foam decomposition products significantly increases the back pressure on the metal stream compared with the conventional open cavity sand mold. Entrapment of the liquid pyrolysis products during the metal filling generates many casting defects, such as internal pores, fold and blisters. Existence of these casting defects sometimes seriously degrades the quality of the components manufactured by the LFC process. Understanding and controlling the metal filling of the LFC process will certainly make this process more robust."

Jan 1, 2004

By Jim Hardy, Tim McKnight

"The thermal mass flow controller, or MFC, has become an instrument of choice for the monitoring and controlling of process gas flow throughout the materials processing industry. In the semiconductor industry, these MFCs are used on over 70% of the processing tools. Reliability and accuracy are major concerns for the users of the MFCs. Calibration and characterization technologies for the development and implementation of mass flow devices are described. Sources of inaccuracy in process gas handling are described, and a model to correct for these inaccuracies is outlined. A gravimetric calibrator is described that allows flow sensors to be calibrated in corrosive, reactive gases to an accuracy of 0.3% of reading, at least an order of magnitude better than previously possible. All described capabilities are implemented in a Department of Energy User Facility which is available to industry and universities to test and develop gas flow sensors and controllers and evaluate their performance related to environmental effects, reliability, reproducibility, and accuracy.IntroductionMaterials processing is at the heart of semiconductor manufacturing. To make today's advanced integrated circuits, silicon wafers are subjected to over 200 process steps. Most of these steps involve processes such as etching, implanting, diffusion, annealing, deposition, and lithography (resist deposition and hardening). Often one or more process gases are used to complete the process step. To achieve the quality and performance required in the micro devices, accurate measurement and control of these gases is essential. The Oak Ridge National Laboratory (ORNL), in conjunction with the semiconductor industry, has been working to improve process gas measurement and control accuracy and reliability. Standardized test methods have been developed to characterize and benchmark the performance of mass flow controllers (MFCs), the method of choice for monitoring and controlling gas delivery. Testbeds have been designed and fabricated to produce repeatable and accurate data using these standards. Baseline testing was performed along with development of a unique mass flow instrument, the gravimetric calibrator."

Jan 1, 1997

By A. V. Tarasov

The proposed process is based on creating a controlled frothed layer of molten slag, in which fine particles of carbonaceous reductant and raw material to be processed are mixed with emulsified iron. Frothing of the slag layer without external blowing occurs as a result of intensive evolution of gaseous reduction products. The froth reaction process is maintained due to the heat of an electric arc in the slag layer. When the metal bath is heated by the arc to 1400- 1 500°C, the low temperature of the slag surface of about 1200-1 300°C is maintained due to low thermal conductivity of slag froth preventing heat loss. In order to maintain the required slag froth level and control the process temperature, air tuyeres are installed above the slag bath; blowing air serves also for oxidation of zinc in fumes and for its transportation. High adsorption and thermal insulating properties of slag froth ensure virtually complete elimination of dust and mist entrainment along with low heat losses. The main macrokinetic regularities of the carbon thermal reduction of zinc-containing slag melts have been studied under frothing conditions. The mechanism of formation of gas-slag emulsion has been identified under the conditions of reaction [C]+[O]=CO occurring locally at the slag-metal interface. It has been demonstrated that under the froth reduction conditions the zinc removal rate from the melt increases on the average by 3 to 5 times. Based on the physical and chemical data obtained, basic principles of the dezincing technology have been developed for different intermediate oxide iron-containing products produced in the process of ferrous and non-ferrous metals production.

Jan 1, 2002

By K. Sanjay

Factorial optimisation technique has been used to develop regression equations at different time intervals for extraction of manganese from precipitated manganese oxide/hydroxide in sulphuric acid using charcoal as the reductant. The three parameters chosen for a 23 full factorial design were : acid concentration, amount of carbon and temperature. The regression equations were used to predict >> 90% extractions as well as kinetic data.

Jan 1, 1996

By O. Forsén

In the first part of this paper is studied the behaviour of small amounts of impurity elements? in the solidification of copper anodes. In the second part the dissolution of these impure anodes in sulphate based electrolysis is discussed. The first part is introduced with practical examples, the .model of solidification of impurities during the solidification of anode copper. According to this model the solidification structures of anode copper are strongly influenced by both thermodynamic and kinetic factors. Thermodynamics determine the microstructure of anode copper, but kinetics can alter the composition of melt to such that there is formed unequilibrium structures during the solidification, especially when the residual melt is solidified. The electrolysis experiments have clarified the behaviour of impuririties in the electrochemical dissolution in sulphate. Based copper electrolysis. In this study it is widely investigated to what extent any impurity elements or oxides will dissolve. In copper electrorefining. With the aid of the electrochemtcal experiments it was possible to fulfil quantitatively the qualitative results accomplished by microstructure studies.

Jan 1, 1985

By Carla Lupi, Mauro Pasquali

"Photographic technology is based on light sensitivity of silver halides that, because of silver properties, are capable of forming photographic images. Photographic laboratories and hospital departments because of digital photographic systems less use this technology today. Nevertheless recovery of silver is still advantageous because environmental problems related to Ag ions danger to biological system. Many processes have been studied to treat silver containing photographic bath: cementation, chemical precipitation and electrowinning. In this work, after preliminary voltammetric tests, a batch electrometallurgical process has been studied to completely deplete the silver containing photographic fixing baths. The effect, of silver concentration in the electrolyte, varying over the range 0,2-1 g/L, bath stirring and current density ranging from 10 to 500 A/m2 on process yield and deposit quality, has been investigated. Introduction Photographic wastes, electronic scrap and spent catalysts constitute the main sources of materials for silver recycling. Among those silver secondary sources, the photographic discharged material could be still important and useful, even if photographic laboratories and hospital departments, because of digital photographic systems, less use photographic technology. Several processes have been developped in order to recover silver used in the field of photography from both photographic solutions and scrap film paper[1-5]. Fixing solutions are very complex baths but, because of silver position in the electromotive series, electrolysis could represent an advantageous method for silver recovery. Electrolysis produces high purity silver without generating new pollutants, while the fixer can be reused: obviously it is necessary to purge off a portion of this solution in order to avoid the excessive build up of other deleterious compounds into solution. A tested recovery method was constituted by the dissolution of silver from X-ray films with concentrated nitric acid. Internal electrolysis and external electrolysis methods were carried out using a steel electrode as cathode and a copper electrode as anode [6]. Silver recovery from photographic chemical solutions has been also performed in a special cell [7]: the solution is supplied to the bottom of a non-agitated cell having a vertically elongated form and including a central anode enclosed by a cathode. An other study discloses the use of an electrolytic cell comprising at least one anodic compartment and one cathodic compartment: the solution is treated in the cathodic compartment and then recycled in the anodic one [8]. A more recent work proposes the use of zirconium cathode for the recovery of silver from photographic fixing solution [9]: studies carried out by cyclic voltammetry showed that about 98% of total Ag can be recovered with an electrical efficiency close to 92%."

Jan 1, 2008